2-amino-5-fluorophenyl cyclopropyl ketone

ABSTRACT

The present invention provides 1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea which has the structural formula I ##STR1## Further provided are compositions and methods comprising that compound for the control of undesirable plant species.

This is a divisional of application Ser. No. 08/236,718 filed on Apr.29, 1994, now U.S. Pat. No. 5,492,884.

BACKGROUND OF THE INVENTION

Weeds cause tremendous global economic losses by reducing crop yieldsand lowering crop quality. In the United States alone, agronomic cropsmust compete with hundreds of weed species. In particular,barnyardgrass, broadleaf weeds and sedges cause extensive economiclosses.

U.S. Pat. No. 5,280,007 discloses certain sulfamoyl urea herbicides.However, that patent does not specifically disclose the compound of thepresent invention.

It is therefore an object of the present invention to provide a compoundwhich is highly effective for controlling undesirable plant species.

It is also an object of the present invention to provide a method forcontrolling undesirable plant species.

These and other objects of the present invention will become moreapparent from the detailed description thereof set forth below.

SUMMARY OF THE INVENTION

The present invention relates to1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea.

This invention also relates to a method for using1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]-sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureato control undesirable plant species.

DETAILED DESCRIPTION OF THE INVENTION

Advantageously, the present invention provides a method for controllingundesirable plant species by applying to the foliage of said plants, orto the soil or water containing seeds or other propagating organsthereof, a herbicidally effective amount of1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea.

Surprisingly, it has been found that among the1-{[2-(cyclopropylcarbonyl)(4-substituted)phenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureacompounds,1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureaprovides a higher level of weed control.

The1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureacompound of the present invention has the following structural formulaI: ##STR2##

Advantageously, it has been found that1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureais especially useful for the selective control of barnyardgrass,broadleaf weeds and sedges in the presence of cereal crops.

1-{[2-(Cyclopropylcarbonyl)-4-fluorophenyl]-sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureamay be prepared by reacting 2-amino-4,6-dimethoxypyrimidine withchlorosulfonyl isocyanate in the presence of methylene chloride followedby treatment of the thus prepared reaction mixture with2-amino-5-fluorophenyl cyclopropyl ketone and triethylamine in thepresence of methylene chloride. The reaction scheme is shown in FlowDiagram I. ##STR3##

The1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureacompound of the present invention is an effective herbicidal agentuseful for the control of a wide variety of undesirable plant species.That compound is effective for controlling weeds native to both dry landand wetland areas. That compound is also useful as an aquatic herbicideand is effective in controlling the above-said undesirable plants whenapplied to the foliage thereof or to the soil or water containing seedsor other propagating organs thereof, such as stolons, tubers orrhizomes, at rates of from about 0.016 to 4.0 kg/ha and preferably fromabout 0.125 to 1.0 kg/ha. Of course, higher rates may be used to equaleffect, but use at such higher rates is deemed to be economicallywasteful and environmentally undesirable.

While the compound of the present invention is effective for controllingundesirable plant species when employed alone, it may also be used incombination with other biological chemicals, including other herbicides.

The compound of this invention may be applied in the form of a solid orliquid herbicidal composition, comprising a herbicidally effectiveamount of the compound dispersed or dissolved in an agronomicallyacceptable solid or liquid carrier. The formulations may be applied aspreemergence or postemergence treatments.

Advantageously,1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)ureamay be formulated as an emulsifiable concentrate, a wettable powder, agranular formulation, a flowable concentrate or the like.

In order to facilitate a further understanding of the invention, thefollowing examples are presented primarily for the purpose ofillustrating more specific details thereof. The invention should not bedeemed limited by the examples as the full scope of the invention isdefined in the claims. The term NMR designates nuclear magneticresonance.

EXAMPLE 1 Preparation of 2-Amino-5-fluorophenyl cyclopropyl ketone##STR4##

4-Fluoroaniline (5.0 g, 45 mmol), cyclopropyl cyanide (5.0 mL, 68 mmol)and aluminum chloride (6.6 g, 49.5 mmol) are added sequentially to amixture of boron trichloride (45 mL of a 1.0M solution in methylenechloride) and 1,2-dichloroethane (50 mL) at 0° C. The reaction mixtureis warmed to room temperature, distilled until the pot temperaturereaches 70° C., refluxed for 18 hours, cooled and diluted with water.The aqueous mixture is extracted with methylene chloride. The organicextracts are combined, dried over anhydrous sodium sulfate andconcentrated in vacuo to give the title product as an orange oil (4.1 g,51%) which is identified by NMR spectral analysis.

Using essentially the same procedure, but employing the appropriatelysubstituted aniline, the following compounds are obtained: ##STR5##

EXAMPLE 2 Preparation of1-{[2-(Cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea##STR6##

Chlorosulfonyl isocyanate (2.0 mL, 3.25 g, 23.0 mmol) is added to asolution of 2-amino-4,6-dimethoxypyrimidine (4.13 g, 26.6 mmol) inmethylene chloride at 0° C. The resulting mixture is stirred for 30minutes and a solution of 2-amino-5-fluorophenyl cyclopropyl ketone(4.77 g, 26.6 mmol) and triethylamine (6.3 mL, 4.57 g, 45.2 mmol) inmethylene chloride is slowly added to the mixture. The resultingsolution is stirred at room temperature for 18 hours, concentrated invacuo and dissolved in methanol. The methanol solution is adjusted toabout pH 1 with 10% hydrochloric acid and extracted with methylenechloride. The combined organic extracts are dried over anhydrous sodiumsulfate and concentrated in vacuo to obtain a residue. Flash columnchromatography of the residue using silica gel and 30% to 50% ethylacetate in hexanes solutions affords a residue which is crystallizedfrom an ether/petroleum ether solution to give the title product as apale yellow solid (2.83 g, 24%, mp 76°-78° C.).

Using essentially the same procedure, but employing the appropriatelysubstituted 2-aminophenyl cyclopropyl ketone, the following compoundsare obtained:

    ______________________________________                                         ##STR7##                                                                            Y      mp °C.                                                   ______________________________________                                               CH.sub.3                                                                             128-133                                                                CH.sub.3 CH.sub.2                                                                    148-150                                                                Cl     152-153                                                         ______________________________________                                    

EXAMPLE 3 Preemergence Herbicidal Evaluations

The preemergence herbicidal activity of the test compounds isexemplified by the following tests in which the seeds of a variety ofmonocotyledonous and dicotyledonous plants are separately mixed withpotting soil and planted on top of approximately one inch of soil inseparate pint containers. After planting, the containers are sprayedwith the selected aqueous acetone solutions containing test compounds insufficient quantity to provide the equivalent of about 0.125 to 1.0 kgper hectare of test compound per container. The treated containers arethen placed on greenhouse benches, watered and cared for in accordancewith conventional greenhouse procedures. From four to five weeks aftertreatment, the tests are terminated and each container is examined andrated according to the rating system set forth below. The data obtainedare reported in Table I.

Test compounds evaluated in this example and in the following exampleare assigned a compound number. Data in Table I are reported by compoundnumber.

Plant species employed in this preemergence evaluation and in thepostemergence evaluation in the following example are reported by headerabbreviation, common name and scientific name.

    ______________________________________                                        PLANT SPECIES EMPLOYED IN HERBICIDAL                                          EVALUATIONS                                                                   Header                                                                        Abb.   Common Name  Scientific Name                                           ______________________________________                                        ABUTH  Velvetleaf   ABUTILON THEOPHRASTI,                                                         MEDIC.                                                    AMBEL  Ragweed,     AMBROSIA ARTEMISIIFOLIA,                                         Common       L.                                                        CAGSE  Bindweed, Hedge                                                                            CALYSTEGIA SEPIUM                                         CHEAL  Lambsquarters,                                                                             CHENOPODIUM ALBUM, L.                                            Common                                                                 IPOSS  Morningglory,                                                                              IPOMOEA SPP.                                                     Spp.                                                                   SINAR  Mustart, Wild                                                                              BRASSICA KABER,                                                               (DC) L. C. WHEELR                                         ECHCG  Barnyardgrass                                                                              ECHINOCHLOA CRUS-GALLI,                                                       (L) BEAU                                                  CYPRO  Nutsedge, Purple                                                                           CYPERUS ROTUNDUS, L                                       SOLNI  Nightshade, Black                                                                          SOLANUM NIGRUM, L.                                        ______________________________________                                    

Herbicide Rating Scale

Results of herbicide evaluation are expressed on a rating scale (0-9).The scale is based upon a visual observation of plant stand, vigor,malformation, size, chlorosis and overall plant appearance as comparedwith an untreated control.

    ______________________________________                                                                  % Control                                           Rating Meaning            Compared to Check                                   ______________________________________                                        9      Complete Kill      100                                                 8      Approaching Complete Kill                                                                        91-99                                               7      Good Herbicidal Effect                                                                           80-90                                               6      Herbicidal Effect  65-79                                               5      Definite Injury    45-64                                               4      Injury             30-44                                               3      Moderate Effect    16-29                                               2      Slight Effect       6-15                                               1      Trace Effect       1-5                                                 0      No Effect          0                                                   --     No Evaluation                                                          ______________________________________                                    

    ______________________________________                                        COMPOUNDS EMPLOYED IN HERBICIDAL                                              EVALUATIONS                                                                   Compound                                                                      Number                                                                        ______________________________________                                        1         1-{[2-(Cyclopropylcarbonyl)-4-fluorophenyl]-                                  sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)-                                   urea                                                                2         1-{[4-Chloro-2-(cyclopropylcarbonyl)phenyl]-                                  sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)-                                   urea                                                                3         1-{[2-(Cyclopropylcarbonyl)-4-methylphenyl]-                                  sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)-                                   urea                                                                4         1-{[2-(Cyclopropylcarbonyl)-4-ethylphenyl]-                                   sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)-                                   urea                                                                ______________________________________                                    

As can be seen from the data in Table I, the compound of the presentinvention,1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea(compound number 1) is a more effective preemergence herbicidal agentthan the comparative compounds (compound numbers 2-4).

                                      TABLE I                                     __________________________________________________________________________    Preemergence Herbicidal Evaluation of Test Compounds                          Compound                                                                            Rate                                                                    Number                                                                              (kg/ha)                                                                            ABUTH                                                                              AMBEL                                                                              CAGSE                                                                              CHEAL                                                                              IPOSS                                                                             SINAR                                                                              SOLNI                                                                              ECHCG                                                                              CYPRO                       __________________________________________________________________________    1     1.000                                                                              9.0  9.0  9.0  9.0  9.0 8.7  9.0  7.0  9.0                               0.500                                                                              8.0  8.0  9.0  9.0  8.0 8.7  9.0  6.5  7.5                               0.250                                                                              7.0  8.0  4.5  8.5  4.5 8.7  8.0  5.5  5.5                               0125 4.5  7.5  4.5  7.0  3.5 8.7  6.7  3.5  3.5                         2     0.500                                                                              2.0  --   --   9.0  0.0 9.0  6.0  0.0  0.0                               0.250                                                                              0.0  0.0  0.0  8.0  0.0 9.0  4.0  0.0  0.0                               0.125                                                                              0.0  0.0  0.0  7.0  0.0 9.0  0.0  0.0  0.0                         3     0.250                                                                              3.0  2.0  --   0.0  2.0 8.0  4.0  2.0  0.0                               0.125                                                                              0.0  0.0  --   --   1.0 8.0  0.0  0.0  0.0                         4     0.250                                                                              0.0  0.0  --   0.0  0.0 0.0  0.0  0.0  0.0                               0.125                                                                              0.0  0.0  --   0.0  0.0 0.0  0.0  0.0  0.0                         __________________________________________________________________________

EXAMPLE 4 Postemergence Herbicidal Evaluations

The postemergence herbicidal activity of the test compounds isdemonstrated by the following tests, wherein a variety of dicotyledonousand monocotyledonous plants are treated with the test compounds,dispersed in aqueous acetone mixtures. In the tests, seedling plants aregrown in jiffy flats for about two weeks. The test compounds aredispersed in 50/50 acetone/water solutions containing 0.5% TWEEN®20, apolyoxyethylene sorbitan monolaurate surfactant of Atlas ChemicalIndustries, in sufficient quantities to provide the equivalent of about0.125 to 1.0 kg per hectare of test compound when applied to the plantsthrough a spray nozzle operating at 40 psi for a predetermined time.After spraying, the plants are placed on greenhouse benches and arecared for in the usual manner, commensurate with conventional greenhousepractices. From four to five weeks after treatment, the seedling plantsare examined and rated according to the rating system provided inExample 3.

The data obtained are reported in Table II. Where more than one test isinvolved for a given compound, the data are averaged. Data in Table IIare reported by compound number.

As can be seen from the data in Table II, the compound of the presentinvention1-{[2-(cyclopropylcarbonyl)-4-fluorophenyl]sulfamoyl}-3-(4,6-dimethoxy-2-pyrimidinyl)urea(compound number 1) is a more effective postemergence herbicidal agentthan the comparative compounds (compound numbers 2-4).

                                      TABLE II                                    __________________________________________________________________________    Postemergence Herbicidal Evaluation of Test Compounds                         Compound                                                                            Rate                                                                    Number                                                                              (kg/ha)                                                                            ABUTH                                                                              AMBEL                                                                              CAGSE                                                                              CHEAL                                                                              IPOSS                                                                             SINAR                                                                              ECHCG                                                                              CYPRO                            __________________________________________________________________________    1     1.000                                                                              9.0  8.0  7.0  4.0  9.0 9.0  5.0  6.0                                    0.500                                                                              9.0  8.0  7.0  2.0  9.0 9.0  4.0  5.0                                    0.250                                                                              9.0  8.0  --   2.0  9.0 9.0  4.0  4.0                                    0.125                                                                              9.0  8.0  --   2.0  9.0 9.0  3.0  4.0                              2     0.500                                                                              8.0  7.0  --   2.0  9.0 9.0  2.0  4.0                                    0.250                                                                              7.0  6.0  --   2.0  8.0 8.0  2.0  2.0                                    0.125                                                                              5.0  5.0  7.0  1.0  7.0 8.0  2.0  --                               3     0.250                                                                              3.0  5.0  --   7.0  4.0 9.0  0.0  0.0                                    0.125                                                                              3.0  5.0  --   7.0  4.0 9.0  0.0  0.0                              4     0.250                                                                              0.0  0.0  --   0.0  0.0 0.0  0.0  0.0                                    0.125                                                                              0.0  0.0  --   0.0  0.0 0.0  0.0  0.0                              __________________________________________________________________________

What is claimed is:
 1. 2-Amino-5-fluorophenyl-cyclopropyl ketone.